Synthesis and characterization of polyaniline doped with organic acids

Spectroscopic [UV–visible and Fourier transform IR (FTIR)] and thermal properties of chemically synthesized polyanilines are found to be affected by varying the protonation media (acetic, citric, oxalic, and tartaric acid). The optical spectra show the presence of a greater fraction of fully oxidized insulating pernigraniline phase in polyaniline doped with acetic acid. In contrast, the selectivity in the formation of the conducting phase is higher in oxalic acid as a protonic acid media. The FTIR spectra of these polymers reveal a higher ratio of the relative intensities of the quinoid to benzenoid ring modes in acetic acid doped polyaniline. Scanning electron micrographs revealed a sponge‐like structure derived from the aggregation of the small granules in acetic acid and oxalic acid doped polyaniline. A three‐step decomposition pattern is observed in all the polymers, regardless of the protonic acid used for the doping. The second step loss related to the loss of dopant is found to be higher in the oxalic acid doped polymer. In accordance with these results the conductivity is also found to be higher in oxalic acid doped material. The temperature dependent conductivity measurements show the thermal activated behavior in all the polymers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2043–2049, 2004     

EPR studies of a molybdenyl complex in single crystals of NH4Cl

Electron paramagnetic resonance of [MoOCl₅]^2? has been studied in single crystals of NH₄Cl. At room temperature the interaction of the unpaired electron with both the even and odd isotopes of molybdenum has been observed. The existence of metal-halogen π bonding is established by the observation of the ligand superhyperfine interaction at liquid nitrogen temperatures. Various possible models corresponding to the different spatial configurations of the molybdenyl complex in the lattice are considered to explain the experimentally observed features. The spectra are analysed using the usual spin-hamiltonian corresponding to tetragonal symmetry. The spin-hamiltonian parameters obtained are: g_∥ = 1.964, g_? = 1.945, A_∥ = 75.53 × 10^?4 cm^?1, A_⊥ = 38.42 × 10^?4 cm^?1.     

A simple spectrophotometric method for determination of isoxsuprine hydrochloride in pharmaceuticals

A spectrophotometric method has been developed for the determination of isoxsuprine hydrochloride and its dosage forms, based on its coupling reaction with diazotized sulphanilic acid. The yellow chromophore has an absorption maximum at 440 nm. Beer's law holds over the range 0.8-8 mu/ml in the final solution.     

Energy transfer from a platinum—nickel excited state to platinum clusters in quasi-one-dimensional Ba(Pt,Ni)(CN)4·nH2O crystals

Laser-induced luminescence in quasi-one-dimensional Ba(Pt, Ni)(CN)₄·nH₂O crystals has been measured from 5 to 300 K. A well-defined luminescence peak is observed, corresponding to an excited electronic state of platinum and nickel. Energy transfer from this Pt—Ni excited state to Pt(CN)₄^2? clusters is found to be very much dependent on the temperature.     

Direct asymmetric organocatalytic Michael reactions of alpha,alpha-disubstituted aldehydes with beta-nitrostyrenes for the synthesis of quaternary carbon-containing products

[reaction: see text] Direct asymmetric catalytic Michael reactions have been performed using chiral-amine/acid bifunctional catalysts. Performed with 0.3 equiv of (S)-(+)-1-(2-pyrrolidinylmethyl)pyrrolidine and 0.3 equiv of trifluoroacetic acid as the catalyst, the reaction of alpha,alpha-dialkylaldehydes with (E)-beta-nitrostyrene provided the alpha,alpha-dialkyl Michael products in up to 96% yield with up to 91% ee. With respect to enantioselectivity, l-proline was a poor catalyst of this class of Michael reactions.     

Synthesis and characterization of sol–gel derived glass-ceramic and its corrosion protection on 316L SS

Glass-ceramic was prepared by sol–gel method using Ca(NO₃)₂·4H₂O and P₂O₅ as Ca and P precursors, respectively. In order to improve the bioactivity of the implant material, glass-ceramic (β-Ca₂P₂O₇) coating was developed on 316L SS substrate by spin coating method. Coating was annealed at different temperatures and its corrosion resistance was evaluated by electrochemical polarization and impedance analysis using Ringer’s solution as electrolyte. The results from the present study, show excellent corrosion resistance for coated 316L SS, corroborated by the high values of charge transfer resistance from impedance analysis and higher breakdown and repassivation potential with the corresponding lower current density from polarization measurements. Based on the results, the glass-ceramic coating on 316L SS can be considered as a corrosion resistant material.     

Ruthenium(II)/(III) complexes of bidentate acetyl hydrazide Schiff bases

A series of octahedral Ru^II/Ru^III complexes of the type [Ru(Y)(CO)(BAX)(PPh₃)₂] and [RuCl₂(BAX)(PPh₃)₂] (Y = H or Cl; BAX = benzaldehydeacetylhydrazone anion; X = H, Me, OMe, OH, Cl or NO₂) have been prepared and characterised by spectral, magnetic and cyclic voltammetric studies. The Ru^II complexes are low spin diamagnetic (S = 0) whereas the Ru^III complexes are low spin and paramagnetic (S = 1/2). These Ru^II and Ru^III complexes absorb in the visible region respectively at ca. 16,000 and 28,000 cm^–1 which bands are assigned to the MLCT. The correlation of the _max values of the Ru^III complexes with the ⁺ Hammett parameter, is linear, indicating the profound effect of substituents on the electron density of the central metal. I.r. spectral data reveals that the hydrazone is chelated to ruthenium through the hydrazinic nitrogen and the deprotonated enolic oxygen. The rhombic nature of the e.s.r. spectra of the Ru^III complexes indicates an asymmetry in the electronic environment around the Ru atom. Ru^II complexes in CH₂Cl₂ show an irreversible Ru^II/III redox couple at ca. 0.9–0.5 V, while the Ru^III complexes show two reversible redox couples in the –0.1–0.1 and 0.8–0.6 V range, indicating that the higher oxidation state of ruthenium is stabilised by hydrazones.     

Simultaneous bioanalysis and pharmacokinetic interaction study of acebrophylline,levocetirizine and pranlukast in Sprague–Dawley rats

The combination of acebrophylline (ABP), levocetirizine (LCZ) and pranlukast (PRN) is used to treat allergic rhinitis, asthma, hay‐fever and other conditions where patients experience difficulty in breathing. This study was carried out with the aim of developing and validating a reverse‐phase high‐performance liquid chromatographic bioanalytical method to simultaneously quantitate ABP, LCZ and PRN in rat plasma. The objective also includes determination of the pharmacokinetic interaction of these three drugs after administration via the oral route after individual and combination treatment in rat. Optimum resolution between the analytes was observed with a C₁₈ Kinetex column (250 mm × 4.6 mm × 5 μm). The chromatography was performed in a gradient elution mode with a 1 mL/min flow rate. The calibration curves were linear over the concentration range of 100–1600 ng/mL. The intra‐ and inter‐day precision and accuracy were found to be within acceptable limits as specified in US Food and Drug Administration guideline for bioanalytical method validation. The analytes were stable on the bench‐top (8 h), after three freeze–thaw cycles, in the autosampler (8 h) and as a dry extract (?80°C for 48 h). The statistical results of the pharmacokinetic study in Sprague–Dawley rats showed a significant change in pharmacokinetic parameters for PRN upon co‐administration of the three drugs.     

CeO2/Pd Nanoparticles Incorporated Fly Ash Zeolite: An Efficient and Recyclable Catalyst for Csp2-Csp2 Bond Formation Reactions

The catalytic activity of CeO₂ and palladium nanoparticles supported fly ash zeolite (CeO₂/Pd@FAZ) for C_sp²-C_sp² bond formation was studied. CeO₂/Pd@FAZ was characterized by FTIR, XRD, EDAX and TEM studies. In the Suzuki-Miyauracross-coupling reaction, biphenyl derivatives with excellent yields were obtained, and the reaction conditions were optimized. The catalytic activity was explored using a wide variety of diversely substituted aryl bromides and chlorides with aryl boronic acid under optimized reaction conditions. The recyclability of the catalyst was established for three cycles, with the conversion rate from 99 to 40%, which gained the advantage of heterogeneous catalysis.